JP2022186352A - Synthetic fiber processing agent and synthetic fiber - Google Patents

Abstract

To improve the convergence of flame-resistant fibers and suppress fluffing of carbon fibers.SOLUTION: A synthetic fiber processing agent contains a phenol amine compound and a nonionic surfactant.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a treatment agent for synthetic fibers and synthetic fibers.

For example, carbon fiber is produced by a spinning process of spinning acrylic resin, etc., a drying and densifying process of drying and densifying the spun fiber, and a carbon fiber precursor, which is a synthetic fiber, by drawing the dried and densified fiber. , a flameproofing treatment step of flameproofing the carbon fiber precursor, and a carbonization treatment step of carbonizing the flameproof fiber.

Synthetic fiber treatment agents are sometimes used in the process of manufacturing synthetic fibers in order to improve the bundling properties of the fibers.
Patent Document 1 discloses a fiber treatment agent as a treatment agent for synthetic fibers containing an amino-modified silicone, a surfactant, and an amine compound having a polyoxyalkylene group and two or more primary amine groups in the molecule. It is

WO2018/003347

By the way, treatment agents for synthetic fibers are required to improve bundling properties of flame-resistant synthetic fibers when synthetic fibers are flame-resistant, and to suppress fluffing of carbon fibers when flame-resistant fibers are carbonized.

The present invention has been made in view of these circumstances, and its object is to provide a treatment agent for synthetic fibers that can improve the bundling property of flame-resistant fibers and suppress the fluffing of carbon fibers. . Another object of the present invention is to provide a synthetic fiber to which this synthetic fiber treatment agent is attached.

The gist of the synthetic fiber treatment agent for solving the above problems is that it contains a phenolamine compound and a nonionic surfactant.
In the synthetic fiber treatment agent, the phenolamine compound is formed from the following phenol derivative, formaldehyde, and polyamine compound, and the following three components: the phenol derivative, formaldehyde, and polyamine compound. It is preferably at least one selected from those obtained by reacting the boron-containing compound with the compound obtained by the reaction.

Phenol derivative: A phenol in which a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less is modified.
In the synthetic fiber treatment agent, the nonionic surfactant contains 1 mol or more and 50 mol or less of an alkylene oxide having 2 or more and 4 or less carbon atoms per 1 mol of a monohydric alcohol having 4 or more and 30 or less carbon atoms. At least one of a compound added at a ratio of 1 mol or more and 50 mol or less in total of an alkylene oxide having 2 or more and 4 or less carbon atoms per 1 mol of an alkylamine having 4 or more and 30 or less carbon atoms. is preferably included.

In the synthetic fiber treatment agent, the mass ratio of the phenolamine compound and the nonionic surfactant is preferably phenolamine compound/nonionic surfactant = 5/95 or more and 95/5 or less. .

The synthetic fiber treatment agent preferably further contains Bronsted acid.
The synthetic fiber treatment agent preferably further contains an epoxy compound.

In the synthetic fiber treatment agent, the epoxy compound preferably contains at least one selected from epoxy-modified silicone and epoxy/polyether-modified silicone.

The synthetic fiber treatment agent preferably further contains at least one selected from amino-modified silicone, dimethyl silicone, and polyether-modified silicone.

In the synthetic fiber treatment agent, the synthetic fiber is preferably a carbon fiber precursor.
The gist of the synthetic fiber treatment agent for solving the above problems is that the synthetic fiber treatment agent is adhered thereto.

ADVANTAGE OF THE INVENTION According to this invention, while being able to improve the bundling property of a flameproof fiber, the fluff of carbon fiber can be suppressed.

(First embodiment)
A first embodiment of a processing agent for synthetic fibers (hereinafter also simply referred to as a processing agent) according to the present invention will be described.

The treatment agent of this embodiment contains a phenolamine compound and a nonionic surfactant.
By containing a phenolamine compound and a nonionic surfactant in the treating agent, when synthetic fibers to which the treating agent is attached are subjected to the flameproofing treatment, bundling of the flameproofed fibers can be improved. In addition, fluffing of the carbon fiber can be suppressed when the flame-resistant fiber is carbonized.

<Regarding the phenolamine compound>
The above phenolamine compound is a compound formed from the following phenol derivative, formaldehyde, and polyamine compound, and a compound formed from the following three components of the phenol derivative, formaldehyde, and polyamine compound, and a boron-containing compound. is preferably at least one selected from those reacted with

Phenol derivative: A phenol in which a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less is modified.
The phenol derivative is preferably represented by Chemical Formula 1 below.

（化１において
Ｒ^１：数平均分子量が１００以上２０００以下の炭化水素基）
上記数平均分子量が１００以上２０００以下の炭化水素基としては、特に制限されないが、例えばプロペン、ブテン、ペンテン、ヘキセン、オクテン、イソブテン、イソペンテン、イソヘキセン、イソオクテン等の重合物からなる炭化水素基が挙げられる。

(R ^{1 in Formula 1} : a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less)
The hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less is not particularly limited. be done.

The number average molecular weight is preferably 500 or more and 1,800 or less, more preferably 600 or more and 1,500 or less.
Only one R ¹ may be modified to phenol, or two or more may be modified to phenol. In the embodiment in which two or more phenols are modified, the same type of hydrocarbon groups may be modified, or different types of hydrocarbon groups may be modified. In addition, the above phenol derivative may have a functional group such as a hydrocarbon group other than R ¹ as long as it has the basic structure of phenol.

The above polyamine compound means an aliphatic hydrocarbon in which two or more primary amino groups are bonded.
The above polyamine compound is preferably represented by Chemical Formula 2 below.

（化２において
Ｘ：０以上１０以下の整数）
ポリアミン化合物の具体例としては、特に制限されないが、例えばエチレンジアミン、ジエチレントリアミン、ジプロピレントリアミン、ジブチレントリアミン、トリエチレンテトラアミン、トリプロピレンテトラアミン、トリブチレンテトラアミン、テトラエチレンペンタアミン、テトラプロピレンペンタアミン、テトラブチレンペンタアミン等が挙げられる。

(In Formula 2, X: an integer of 0 or more and 10 or less)
Specific examples of polyamine compounds include, but are not limited to, ethylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tripropylenetetraamine, tributylenetetraamine, tetraethylenepentamine, and tetrapropylenepentamine. , tetrabutylene pentamine and the like.

One of the above polyamine compounds may be used alone, or two or more of them may be used in combination.
The phenolamine compound is preferably formed by a Mannich reaction between a phenol derivative, formaldehyde, and a polyamine compound.

The phenolamine compound is preferably represented by Chemical Formula 3 or Chemical Formula 4 below.

（化３において
Ｒ^２：数平均分子量が１００以上２０００以下の炭化水素基
Ｘ：０以上１０以下の整数）

(In Formula 3, R ² : a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less X: an integer of 0 or more and 10 or less)

（化４において
Ｒ^３：数平均分子量が１００以上２０００以下の炭化水素基
Ｒ^４：数平均分子量が１００以上２０００以下の炭化水素基
Ｘ：０以上１０以下の整数）
上記フェノールアミン化合物は、上記の化３、又は化４の一方を単独で含有したものであってもよいし、化３と化４の両方を含有したものであってもよい。すなわち、フェノールアミン化合物は、化３と化４の混合物であってもよい。

(In Formula 4, R ³ : a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less R ⁴ : a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less X: an integer of 0 or more and 10 or less)
The phenolamine compound may contain either one of Chemical Formula 3 or Chemical Formula 4 alone, or may contain both Chemical Formula 3 and Chemical Formula 4. That is, the phenolamine compound may be a mixture of chemical formulas 3 and 4.

Also, the phenolamine compound may be a compound formed from three components of a phenol derivative, formaldehyde, and a polyamine compound and reacted with a boron-containing compound. For example, a boron-containing compound may be reacted with Chemical Formula 3 or Chemical Formula 4 above.

In other words, the phenolamine compound may be a borated phenolamine compound. Also, a mixture of a non-boronated phenolamine compound such as the above chemical formulas 3 and 4 and a borated phenolamine compound may be used.

Examples of the boron-containing compound include, but are not particularly limited to, boron oxide, boron halide, boric acid, boric anhydride, and borate ester.
The above boron compounds may be used singly or in combination of two or more.

The ratio of the phenol derivative, formaldehyde, and polyamine compound when forming the phenolamine compound is not particularly limited, and the ratio can be adjusted as appropriate.

As for the ratio of the phenol derivative, formaldehyde, and polyamine compound, for example, 0.7 to 3.5 equivalents of formaldehyde and 0.3 to 1.5 equivalents of polyamine compound are allowed to react with 1 equivalent of the phenol derivative. is preferred.

Further, when the phenolamine compound is obtained by reacting a boron-containing compound with a compound formed from three components of a phenol derivative, formaldehyde, and a polyamine compound, the ratio of the boron-containing compound is not particularly limited, The ratio can be adjusted as appropriate for the reaction.

As for the ratio of the boron-containing compound, for example, it is preferable to react the boron-containing compound with the phenolamine compound so that the boron content is 0.05% by mass or more and 1.5% by mass or less.

The above chemical formulas 3 and 4 as phenolamine compounds and those reacted with a boron-containing compound can be identified using, for example, a liquid chromatography-mass spectrometer (LC-MS).

<About the diluent>
As described below, the phenolamine compound is preferably used as a solution diluted with a diluent when mixed with a nonionic surfactant or the like to prepare a treatment agent.

Examples of diluents include water, organic solvents, mineral oils and the like. Specific examples of organic solvents include hexane, ethanol, isopropanol, ethylene glycol, propylene glycol, diethyl ether, toluene, xylene, dimethylformamide, methyl ethyl ketone and chloroform. Mineral oils include, for example, aromatic hydrocarbons, paraffinic hydrocarbons, naphthenic hydrocarbons, and the like. More specific examples include spindle oil and liquid paraffin. The mineral oil preferably has a viscosity of 80 to 190 redwood seconds. Commercially available products can be appropriately used as these mineral oils.

There is no restriction on the content ratio of the phenolamine compound and the diluent. Assuming that the total content of the phenolamine compound and the diluent is 100 parts by mass, the phenolamine compound can be contained at a rate of 30% by mass or more and 90% by mass or less and the diluent at a rate of 10% by mass or more and 70% by mass or less. More preferably, the content of the phenolamine compound is 40% by mass or more and 80% by mass or less, and the diluent is more preferably 20% by mass or more and 60% by mass or less.

<About nonionic surfactant>
The nonionic surfactant is not particularly limited, but a total of 1 mol or more and 50 mol or less of an alkylene oxide having 2 or more and 4 or less carbon atoms per 1 mol of a monohydric alcohol having 4 or more and 30 or less carbon atoms. At least one of a compound added and a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms in a total ratio of 1 to 50 moles per 1 mol of alkylamine having 4 to 30 carbon atoms. is preferred.

The monohydric alcohol having 4 to 30 carbon atoms may be either an aliphatic alcohol having a linear or branched structure or an aromatic alcohol. Moreover, any of primary alcohol, secondary alcohol, and tertiary alcohol may be used.

Specific examples of monohydric alcohols having 4 to 30 carbon atoms include (1) butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, and hexadecanol. straight-chain alkyl alcohols such as nol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptakosanol, octacosanol, nonacosanol, and triacontanol , (2) isobutanol, isohexanol, 2-ethylhexanol, isononanol, isodecanol, isododecanol, isotridecanol, isotetradecanol, isotriacontanol, isohexadecanol, isoheptadecanol, isooctane Decanol, isononadecanol, isoeicosanol, isoheneicosanol, isodocosanol, isotrichosanol, isotetracosanol, isopentacosanol, isohexacosanol, isoheptacosanol, isooctacosanol , isononacosanol, branched alkyl alcohols such as isopentadecanol, (3) linear alkenyl alcohols such as tetradecenol, hexadecenol, heptadecenol, octadecenol, and nonadecenol, (4) isohexadecenol, isooctadecenol, etc. branched alkenyl alcohols, (5) cyclic alkyl alcohols such as cyclopentanol and cyclohexanol, (6) aromatic alcohols such as phenol, nonylphenol, benzyl alcohol, monostyrenated phenol, distyrenated phenol, and tristyrenated phenol mentioned.

The alkylamine having 4 to 30 carbon atoms is not particularly limited, and may be any of primary amine, secondary amine and tertiary amine.
In the alkylamine having 4 to 30 carbon atoms, the alkyl group having 4 to 30 carbon atoms may be a linear or branched alkyl group. Moreover, it may be a saturated alkyl group or an unsaturated alkyl group.

Specific examples of linear alkyl groups include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl groups. , heptadecyl group, octadecyl group, icosyl group and the like.

Specific examples of branched saturated alkyl groups include isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, iso Pentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group, isoicosyl group and the like can be mentioned.

The unsaturated alkyl group may be an alkenyl group having one double bond as an unsaturated carbon bond, or an alkadienyl group or alkatrienyl group having two or more double bonds. Alternatively, an alkynyl group having one triple bond as an unsaturated carbon bond, an alkadiynyl group having two or more triple bonds, or the like may be used. Specific examples of linear unsaturated alkyl groups having one double bond in the hydrocarbon group include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl group, heptadecenyl group, octadecenyl group, icosenyl group and the like.

Specific examples of branched unsaturated alkyl groups having one double bond in the alkyl group include isooctenyl, isononenyl, isodecenyl, isoundecenyl, isododecenyl, isotridecenyl and isotetradecenyl groups. , isopentadecenyl group, isohexadecenyl group, isoheptadecenyl group, isooctadecenyl group, isoicosenyl group and the like.

Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide. Among these, those containing ethylene oxide are preferable.

The polymerization sequence of alkylene oxide is not particularly limited, and may be a random adduct or a block adduct.
The alkylene oxides having 2 to 4 carbon atoms may be used singly or in combination of two or more.

The number of moles of alkylene oxide added indicates the number of moles of alkylene oxide per 1 mole of alcohol in the starting material.
Although the mass ratio of the phenolamine compound and the nonionic surfactant is not particularly limited, it is preferably phenolamine compound/nonionic surfactant=5/95 or more and 95/5 or less.

<About Bronsted acid>
The treatment agent of the present embodiment preferably further contains a Bronsted acid.
By containing Bronsted acid, the bundling property of the flameproof fibers can be further improved.

Here, Bronsted acid is intended to mean an acid that has protons and can release or dissociate the protons in a water-containing liquid composition. It is intended to be different from acids that do not have protons, such as Lewis acids.

Specific examples of the Bronsted acid are not particularly limited, but for example, acetic acid, alkyl ether acetic acid such as polyoxyethylene (n=10) lauryl ether acetic acid, polyoxyethylene (n=4.5) lauryl ether acetic acid, oleoyl Sarcosinate, lauroyl sarcosinate, phosphoric acid esters of ethylene oxide 5-mol adducts of tridecyl alcohol, phosphoric acid esters such as hexadecyl phosphoric acid esters, lactic acid, citric acid, phosphoric acid, alkylbenzenes such as dodecylbenzenesulfonic acid Sulfonic acid, sulfuric acid and the like can be mentioned.

The Bronsted acids may be used singly or in combination of two or more.
The content of Bronsted acid in the treatment agent is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less.

<About epoxy compounds>
The treatment agent of the present embodiment preferably further contains an epoxy compound.
By containing an epoxy compound, when synthetic fibers to which a treatment agent is attached are used to produce carbon fibers, fluffing of the carbon fibers can be suitably suppressed.

The epoxy compound is not particularly limited, and preferably contains at least one selected from epoxy-modified silicone and epoxy/polyether-modified silicone.

When the epoxy compound contains at least one selected from the above-mentioned epoxy-modified silicone and epoxy-polyether-modified silicone, it is possible to more preferably suppress fluff of the carbon fibers.

Specific examples of the epoxy compound include, for example, a side chain type alicyclic epoxy-modified silicone having a kinematic viscosity at 25°C of 6000 ^{mm 2} /s and an equivalent weight of 3700 g/mol; a side chain type glycidyl epoxy-modified silicone having a kinematic viscosity of 3300 g/mol; a kinematic viscosity at 25°C of 120 ^{mm 2} /s; an equivalent weight of 2700 g/mol; A side chain type glycidyl epoxy polyether-modified silicone having an equivalent weight of 2800 g/mol, a kinematic viscosity of 5000 mm ² /s at 25°C, a side chain type alicyclic epoxy-modified silicone having an equivalent weight of 4200 g/mol, and a kinematic viscosity at 25°C. is 3100 mm ² /s and the equivalent weight is 10200 g/mol side chain type glycidyl epoxy polyether modified silicone, bisphenol A diglycidyl ether (average molecular weight 370), bisphenol A diglycidyl ether (average molecular weight 470), bisphenol F diglycidyl ether (average molecular weight: 340), tetraglycidyldiaminodiphenylmethane, glycidyl etherate of polyglycerin (average molecular weight: 1000), and the like.

The epoxy compounds may be used singly or in combination of two or more. The kinematic viscosity at 25°C of an epoxy compound or the like can be measured by a known method under conditions of 25°C using a Canon Fenske viscometer.

Although the content of the epoxy compound in the treatment agent is not particularly limited, it is preferably 1% by mass or more and 50% by mass or less, and more preferably 3% by mass or more and 20% by mass or less.
<About other silicones>
The treatment agent preferably further contains a silicone other than the epoxy-modified silicone and the epoxy/polyether-modified silicone (hereinafter also referred to as "other silicone"). By containing other silicones, as described later, the strength of carbon fibers produced using synthetic fibers to which a treatment agent is attached can be further improved.

In addition, the treatment agent contains other silicone and the above-mentioned epoxy compound, so that when carbon fibers are produced using synthetic fibers to which the treatment agent is attached, the carbon fibers are more preferably fused together. can be suppressed.

The other silicone is preferably at least one selected from amino-modified silicone, dimethyl silicone, and polyether-modified silicone.
Specific examples of other silicones include, for example, a diamine-type amino-modified silicone having a kinematic viscosity at 25° C. of ²⁵⁰ mm ² /s and an equivalent weight of 7600 g/mol; mol, a monoamine-type amino-modified silicone having a kinematic viscosity at 25° C. of 1700 mm ² /s and an equivalent weight of 3800 g/mol, a kinematic viscosity at 25° C. of 80 mm ² /s and an equivalent weight of 4000 g/ mol of diamine-type amino-modified silicone, dimethyl silicone with kinematic viscosity at 25°C of 5000 mm ² /s, kinematic viscosity at 25°C of 1700 mm ² /s, ethylene oxide/propylene oxide = 40/60, silicone/polyether mass ratio = 20/80 polyether-modified silicone and the like.

(Second embodiment)
A second embodiment of the synthetic fiber according to the present invention will be described. The synthetic fiber of this embodiment is a synthetic fiber to which the treatment agent of the first embodiment is attached. Specific examples of synthetic fibers are not particularly limited, and include (1) polyester fibers such as polyethylene terephthalate, polypropylene terephthalate and polylactate; (4) polyolefin fibers such as polyethylene and polypropylene; (5) cellulose fibers; and (6) lignin fibers.

As the synthetic fiber, a resin-made carbon fiber precursor that becomes a carbon fiber through a carbonization treatment step described later is preferable. The resin constituting the carbon fiber precursor is not particularly limited, but examples thereof include acrylic resins, polyethylene resins, phenol resins, cellulose resins, lignin resins, and pitch.

Although there is no particular limitation on the proportion of the treatment agent of the first embodiment attached to the synthetic fibers, it is preferable to attach the treatment agent (not containing a solvent) to the synthetic fibers in an amount of 0.1 to 2% by mass. , 0.3 to 1.2% by mass.

Examples of the form in which the processing agent of the first embodiment is attached to the fibers include an organic solvent solution, an aqueous liquid, and the like.
As a method for attaching the treatment agent to the synthetic fibers, for example, a known method such as a dipping method, a spray method, a roller method, or a metering pump is applied using an organic solvent solution, an aqueous solution, or the like of the treatment agent of the first embodiment. A method of adhering by the guide lubrication method or the like used can be applied.

A treatment agent according to the present invention and a method for producing carbon fibers using synthetic fibers to which the treatment agent is attached will be described.
The method for producing the carbon fiber preferably includes steps 1 to 3 below.

Step 1: A spinning step in which synthetic fibers are spun and the treatment agent of the first embodiment is attached.
Step 2: A flameproofing step of converting the synthetic fiber obtained in the step 1 into a flameproof fiber in an oxidizing atmosphere at 200 to 300°C, preferably 230 to 270°C.

Step 3: A carbonization step of further carbonizing the flame-resistant fiber obtained in the step 2 in an inert atmosphere at 300 to 2000°C, preferably 300 to 1300°C.
The spinning process further includes a wet spinning process of dissolving a resin in a solvent and spinning, a dry densification process of drying and densifying the wet-spun synthetic fibers, and a drawing process of drawing the dry densified synthetic fibers. It is preferable to have

The temperature of the dry densification step is not particularly limited, but it is preferable to heat the synthetic fibers that have undergone the wet spinning step at, for example, 70 to 200°C. The timing of applying the treatment agent to the synthetic fibers is not particularly limited, but it is preferably between the wet spinning process and the dry densification process.

The oxidizing atmosphere in the flameproofing treatment step is not particularly limited, and for example, an air atmosphere can be adopted.
The inert atmosphere in the carbonization treatment step is not particularly limited, and for example, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or the like can be adopted.

According to the treatment agent and synthetic fiber of the present embodiment, the following effects can be obtained.
(1) The treatment agent contains a phenolamine compound and a nonionic surfactant. Therefore, when the synthetic fibers to which the treating agent is attached are subjected to the flameproofing treatment, the bundling property of the flameproofing fibers can be improved. In addition, fluffing of the carbon fiber can be suppressed when the flame-resistant fiber is carbonized.

(2) The treating agent further contains Bronsted acid. Therefore, the bundling property of the flameproof fibers can be further improved.
(3) The treating agent contains an epoxy compound. Therefore, when carbon fibers are produced using synthetic fibers to which the treatment agent is attached, fluffing of the carbon fibers can be suitably suppressed.

(4) The treatment agent contains other silicones and epoxy compounds. Therefore, when carbon fibers are manufactured using synthetic fibers to which a treatment agent is attached, it is possible to more preferably suppress fusion between carbon fibers.

The above embodiment can be implemented with the following modifications. The above embodiments and the following modifications can be combined with each other within a technically consistent range.
- In the present embodiment, the treatment agent is attached to the synthetic fibers between the wet spinning process and the dry densification process, but the present invention is not limited to this aspect. The treating agent may be attached to the synthetic fibers between the drying densification step and the drawing step, or the treating agent may be attached to the synthetic fibers between the drawing step and the flameproofing step.

- In the present embodiment, for example, the synthetic fiber may be a fiber that is subjected to the flameproofing treatment, but is not subjected to the carbonization treatment. Also, the fiber may be a fiber that is not subjected to both the flameproofing treatment step and the carbonization treatment step.

・The processing agent of the present embodiment contains a stabilizer, an antistatic agent, an antistatic agent, a binder, an antioxidant, and an ultraviolet absorber to maintain the quality of the processing agent within a range that does not impede the effects of the present invention. Ingredients commonly used in treatment agents, such as agents and antifoaming agents (silicone compounds), may also be added.

Examples will be given below in order to make the configuration and effect of the present invention more specific, but the present invention is not limited to these examples. In the following examples and comparative examples, "part" means "mass part" and "%" means "mass%".

Test category 1 (preparation of treatment agents for synthetic fibers)
(Example 1)
A solution (A-1) of a phenolamine compound containing 70 parts of the phenolamine compound (a1-1) and 30 parts of the diluent (a2-1) shown in Table 1 was prepared by the following method. did.

<Solution of phenolamine compound (A-1)>
First, 800 parts (1 equivalent) of a phenol modified with a polybutenyl group where the polybutene portion has a number average molecular weight of 1500, 52 parts (0.7 equivalent) of triethylenetetramine, and 368 parts of mineral oil of 100 redwood seconds. mixed with. To the resulting mixture, 30 parts of a 50% formaldehyde aqueous solution (equivalent to 15 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-1).

Phenolamine compound solutions (A-2) to (A-12) were prepared by the following method.
<Solution of phenolamine compound (A-2)>
100 parts of the phenolamine compound solution (A-1) was reacted with 1.1 parts of boric acid to prepare a phenolamine compound solution (A-2) having a boron content of 0.2% by mass.

<Solution of phenolamine compound (A-3)>
730 parts (1 equivalent) of a phenol modified with polybutenyl groups where the polybutene portion has a number average molecular weight of 1200, 58 parts (1 equivalent) of diethylenetriamine, and 530 parts of 80 redwood second liquid paraffin were mixed. To the resulting mixture, 34 parts of a 50% formaldehyde aqueous solution (equivalent to 17 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-3).

<Solution of phenolamine compound (A-4)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups where the polybutene portion has a number average molecular weight of 600, 102 parts (0.6 equivalent) of triethylenetetraamine, and 916 parts of 150 redwood second mineral oil. Mixed. To the resulting mixture, 70 parts of a 50% formaldehyde aqueous solution (equivalent to 35 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-4).

<Solution of phenolamine compound (A-5)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups where the polybutene portion has a number average molecular weight of 1500, 47 parts (0.5 equivalent) of tripropylenetetraamine, and 213 parts of 100 redwood second liquid paraffin. Mixed. To the resulting mixture, 30 parts of a 50% formaldehyde aqueous solution (equivalent to 15 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-5).

<Solution of phenolamine compound (A-6)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups wherein the polybutene portion has a number average molecular weight of 1500, 66 parts (0.9 equivalent) of triethylenetetraamine, and 872 parts of 120 redwood second mineral oil. Mixed. To the resulting mixture, 30 parts of a 50% formaldehyde aqueous solution (equivalent to 15 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-6).

<Solution of phenolamine compound (A-7)>
100 parts of the phenolamine compound solution (A-6) was reacted with 5.7 parts of boric acid to prepare a phenolamine compound solution (A-7) having a boron content of 1.0% by mass.

<Solution of phenolamine compound (A-8)>
800 parts (1 equivalent) of a phenol modified with polyisobutenyl groups wherein the polyisobutylene portion has a number average molecular weight of 900, 130 parts (1.1 equivalent) of triethylenetetramine, and 1410 parts of 190 redwood second mineral oil were mixed. To the resulting mixture, 150 parts of a 50% formaldehyde aqueous solution (equivalent to 75 parts of formaldehyde, 3.1 equivalents) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-8).

<Solution of phenolamine compound (A-9)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups wherein the polybutene portion has a number average molecular weight of 600, 175 parts (0.8 equivalent) of tetraethylenepentamine, and 423 parts of 100 redwood second mineral oil. Mixed. To the resulting mixture, 62 parts of a 50% formaldehyde aqueous solution (equivalent to 31 parts of formaldehyde, 0.9 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-9).

<Solution of phenolamine compound (A-10)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups where the polybutene portion has a number average molecular weight of 1000, 31 parts (0.7 equivalent) of ethylenediamine, and 840 parts of 120 redwood second mineral oil were mixed. To the resulting mixture, 44 parts of a 50% formaldehyde aqueous solution (equivalent to 22 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-10).

<Solution of phenolamine compound (A-11)>
800 parts (1 equivalent) of a phenol modified with polypropenyl groups wherein the polypropylene portion has a number average molecular weight of 1500; 30 parts of a 50% formaldehyde aqueous solution (equivalent to 15 parts of formaldehyde, 1 equivalent) was added dropwise to the resulting mixture over 1 hour, and then reacted at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-11).

<Solution of phenolamine compound (A-12)>
800 parts (1 equivalent) of octyl-modified phenol, 260 parts (0.7 equivalent) of diethylenetriamine, and 871 parts of 120 redwood second mineral oil were mixed. After 276 parts of a 50% formaldehyde aqueous solution (equivalent to 108 parts of formaldehyde, 1 equivalent) was added dropwise to the resulting mixture over 1 hour, the mixture was reacted at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-12).

The type and content of the phenolamine compound and the type and content of the diluent are as shown in the "phenolamine compound" column and the "diluent" column of Table 1, respectively.

（フェノールアミン化合物）
ａ１－１：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物
ａ１－２：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物をホウ酸と反応させた化合物（ホウ素含有量：０．２質量％）
ａ１－３：ポリブテン部分の数平均分子量が１２００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／ジエチレントリアミンを反応させて得られた化合物
ａ１－４：ポリブテン部分の数平均分子量が６００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物
ａ１－５：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリプロピレンテトラアミンを反応させて得られた化合物
ａ１－６：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物
ａ１－７：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物をホウ酸と反応させた化合物（ホウ素含有量：１．０質量％）
ａ１－８：ポリイソブチレン部分の数平均分子量が９００であるポリイソブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物
ａ１－９：ポリブテン部分の数平均分子量が６００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／テトラエチレンペンタアミンを反応させて得られた化合物
ａ１－１０：ポリブテン部分の数平均分子量が１０００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／エチレンジアミンを反応させて得られた化合物
ａ１－１１：ポリプロピレン部分の数平均分子量が１５００であるポリプロペニル基で変性されたフェノール／ホルムアルデヒド／トリブチレンテトラアミンを反応させて得られた化合物
ａ１－１２：オクチル基で変性されたフェノール／ホルムアルデヒド／ジエチレントリアミンを反応させて得られた化合物
（希釈剤）
ａ２－１：鉱物油（レッドウッド粘度計での粘度が１００秒）
ａ２－２：流動パラフィン（レッドウッド粘度計での粘度が８０秒）
ａ２－３：鉱物油（レッドウッド粘度計での粘度が１５０秒）
ａ２－４：流動パラフィン（レッドウッド粘度計での粘度が１００秒）
ａ２－５：鉱物油（レッドウッド粘度計での粘度が１２０秒）
ａ２－６：鉱物油（レッドウッド粘度計での粘度が１９０秒）
次に、表２に示される各成分を用いて、フェノールアミン化合物の溶液（Ａ－１）が６０部、非イオン性界面活性剤（Ｂ１－１）が２０部、ブレンステッド酸（Ｃ－１）が０．５部、エポキシ化合物（Ｄ－１）が７．５部、その他のシリコーン（Ｅ－１）が１０部、その他化合物が２部となるようにビーカーに加えた。これらをよく撹拌して合成繊維用処理剤を調製した。

(Phenolamine compound)
a1-1: A compound obtained by reacting phenol/formaldehyde/triethylenetetramine modified with a polybutenyl group having a polybutene moiety with a number average molecular weight of 1,500 a1-2: A polybutene moiety having a number average molecular weight of 1,500 A compound obtained by reacting a compound obtained by reacting phenol/formaldehyde/triethylenetetraamine modified with a polybutenyl group and reacting it with boric acid (boron content: 0.2% by mass)
a1-3: A compound obtained by reacting phenol/formaldehyde/diethylenetriamine modified with a polybutenyl group whose polybutene moiety has a number average molecular weight of 1200 a1-4: A polybutenyl group whose polybutene moiety has a number average molecular weight of 600 Compound obtained by reacting modified phenol/formaldehyde/triethylenetetramine a1-5: phenol/formaldehyde/tripropylenetetramine modified with a polybutenyl group having a polybutene moiety with a number average molecular weight of 1,500 was reacted. Compound a1-6 obtained by reacting polybutenyl group-modified phenol/formaldehyde/triethylenetetramine having a polybutene moiety with a number average molecular weight of 1500 a1-7: Number average polybutene moiety A compound obtained by reacting a compound obtained by reacting polybutenyl group-modified phenol/formaldehyde/triethylenetetramine having a molecular weight of 1500 with boric acid (boron content: 1.0% by mass)
a1-8: A compound obtained by reacting phenol/formaldehyde/triethylenetetramine modified with a polyisobutenyl group having a polyisobutylene moiety with a number average molecular weight of 900 a1-9: A polybutene moiety having a number average molecular weight of 600 Compound obtained by reacting phenol/formaldehyde/tetraethylenepentamine modified with a certain polybutenyl group a1-10: Reaction of phenol/formaldehyde/ethylenediamine modified with a polybutenyl group having a polybutene moiety with a number average molecular weight of 1000 Compound a1-11 obtained by reacting polypropenyl group-modified phenol/formaldehyde/tributylene tetraamine in which the polypropylene portion has a number average molecular weight of 1500 a1-12: Compound obtained by reacting with octyl group Compound obtained by reacting modified phenol/formaldehyde/diethylenetriamine (diluent)
a2-1: Mineral oil (viscosity with Redwood viscometer is 100 seconds)
a2-2: Liquid paraffin (viscosity with Redwood viscometer is 80 seconds)
a2-3: Mineral oil (viscosity in Redwood viscometer is 150 seconds)
a2-4: liquid paraffin (viscosity of 100 seconds with a Redwood viscometer)
a2-5: Mineral oil (viscosity on Redwood viscometer is 120 seconds)
a2-6: Mineral oil (190 seconds viscosity with Redwood viscometer)
Next, using each component shown in Table 2, 60 parts of phenolamine compound solution (A-1), 20 parts of nonionic surfactant (B1-1), Bronsted acid (C-1 ), 7.5 parts of epoxy compound (D-1), 10 parts of other silicone (E-1), and 2 parts of other compounds were added to a beaker. These were thoroughly stirred to prepare a synthetic fiber treatment agent.

(Examples 2 to 26 and Comparative Examples 1 to 3)
A solution of each phenolamine compound of Examples 2 to 26 and Comparative Examples 1 to 3 was prepared in the same manner as in Example 1 using each component shown in Tables 1 and 2. Type and content of phenolamine compound solution, type and content of nonionic surfactant, type and content of Bronsted acid, type and content of epoxy compound, and other silicones in the treatment agent of each example The type and content of other compounds, the type and content of other compounds, and the mass ratio of the succinimide compound and the nonionic surfactant are shown in Table 2, "Solution of phenolamine compound" column, ” column, “Bronsted acid” column, “epoxy compound” column, “other silicone” column, “other compound” column, and “succinimide compound / nonionic surfactant” column, respectively. .

表２の記号欄に記載するＢ１－１～Ｂ１－９、Ｂ２－１～Ｂ２－３、Ｃ－１～Ｃ－１１、Ｄ－１～Ｄ－１１、Ｅ－１～Ｅ－６、Ｆ－１～Ｆ－５の各成分の詳細は以下のとおりである。

B1-1 to B1-9, B2-1 to B2-3, C-1 to C-11, D-1 to D-11, E-1 to E-6, F- described in the symbol column of Table 2 The details of each component of 1 to F-5 are as follows.

(Nonionic surfactant)
B1-1: Compound obtained by adding 9 mol of ethylene oxide to 1 mol of dodecyl alcohol B1-2: Compound obtained by adding 12 mol of ethylene oxide to 1 mol of isododecyl alcohol B1-3: 1 mol of tetradecyl alcohol B1-4: Compound obtained by adding 7 mol of ethylene oxide to 1 mol of tetradecyl alcohol B1-5: 15 mol of ethylene oxide to 1 mol of pentadecyl alcohol Added compound B1-6: Compound obtained by adding 15 mol of ethylene oxide to 1 mol of tetradecyl alcohol and then adding 18 mol of propylene oxide B1-7: Ethylene to 1 mol of secondary tridecyl alcohol Compound to which 9 mol of oxide was added B1-8: Compound to which 2 mol of ethylene oxide and 6 mol of propylene oxide were randomly added to 1 mol of dodecyl alcohol B1-9: Ethylene oxide to 1 mol of tristyrenated phenol 15 mol of and 9 mol of propylene oxide are added B2-1: A compound in which 4 mol of ethylene oxide is added to 1 mol of dodecylamine B2-2: 8 mol of ethylene oxide is added to 1 mol of dodecylamine Compound B2-3: A compound obtained by adding 15 mol of ethylene oxide to 1 mol of octadecylamine (Bronsted acid)
C-1: acetic acid C-2: polyoxyethylene (n = 10) lauryl ether acetic acid C-3: polyoxyethylene (n = 4.5) lauryl ether acetic acid C-4: oleoyl sarcosinate C-5: Lauroyl sarcosinate C-6: phosphate ester of tridecyl alcohol ethylene oxide 5 mole adduct C-7: hexadecyl phosphate ester C-8: lactic acid C-9: citric acid C-10: phosphoric acid C- 11: Dodecylbenzenesulfonic acid (epoxy compound)
D-1: Side chain type alicyclic epoxy-modified silicone having a kinematic viscosity at 25°C of 6000 mm ² /s and an equivalent weight of 3700 g/mol D-2: A kinematic viscosity at 25°C of 8000 mm ² /s and an equivalent weight of 3300 g/mol mol side chain type glycidyl epoxy-modified silicone D-3: kinematic viscosity at 25° C. is 120 mm ² /s and equivalent weight is 2700 g/mol double-ended glycidyl epoxy-modified silicone D-4: kinematic viscosity at 25° C. is 2800 mm ² /s, equivalent weight is 2800 g/mol side chain type glycidyl epoxy polyether-modified silicone D-5: side chain type alicyclic epoxy-modified silicone with kinematic viscosity at 25° C. of 5000 mm ² /s and equivalent weight of 4200 g/mol Silicone D-6: Side chain type glycidyl epoxy polyether-modified silicone having a kinematic viscosity at 25°C of 3100 mm ² /s and an equivalent weight of 10200 g/mol D-7: Bisphenol A diglycidyl ether (average molecular weight 370)
D-8: bisphenol A diglycidyl ether (average molecular weight 470)
D-9: Bisphenol F diglycidyl ether (average molecular weight 340)
D-10: Tetraglycidyldiamine diphenylmethane D-11: Glycidyl etherate of polyglycerin (average molecular weight 1000)
(other silicones)
E-1: A diamine-type amino-modified silicone having a kinematic viscosity at 25°C of 250 mm ² /s and an equivalent weight of 7600 g/mol E-2: A kinematic viscosity at 25°C of 1300 mm ² /s and an equivalent weight of 1700 g/mol Diamine-type amino-modified silicone E-3: Monoamine-type amino-modified silicone with a kinematic viscosity of 1700 mm ² /s at 25°C and an equivalent weight of 3800 g/mol E-4: Kinematic viscosity at 25°C of 80 mm ² /s and an equivalent diamine type amino-modified silicone E-5: dimethyl silicone having a kinematic viscosity of 5000 mm ² /s at 25° C. E-6: kinematic viscosity of 1700 mm ² /s at 25° C., ethylene oxide/propylene oxide = 40/60, polyether-modified silicone with a silicone/polyether mass ratio of 20/80 (Other compounds)
F-1: Polyethylene glycol having a molecular weight of 600 with 3-aminopropyl groups added to both ends F-2: Didodecyl ester of a bisphenol A ethylene oxide 2-mol adduct F-3: 1-ethyl-2-( heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium ethyl sulfate F-4: trimethyloctylammonium dimethyl phosphate F-5: isotridecyl isostearate Test category 2 ( manufacturing of synthetic fibers and carbon fibers)
Synthetic fibers and carbon fibers were produced using the synthetic fiber treatment agent prepared in Test Section 1.

First, as step 1, an acrylic resin was wet-spun. Specifically, a copolymer composed of 95% by mass of acrylonitrile, 3.5% by mass of methyl acrylate, and 1.5% by mass of methacrylic acid and having an intrinsic viscosity of 1.80 was dissolved in dimethylacetamide (DMAC) to give a polymer concentration of was 21.0% by mass and a spinning dope having a viscosity of 500 poise at 60°C was prepared. The spinning stock solution was discharged from a spinneret with a hole diameter (inner diameter) of 0.075 mm and a hole number of 12,000 at a draft ratio of 0.8 into a coagulation bath of 70 mass % aqueous solution of DMAC kept at a spinning bath temperature of 35°C.

The coagulated yarn was desolvated in a washing tank and simultaneously stretched 5 times to prepare a water-swollen acrylic fiber strand (raw material fiber). The synthetic fiber treatment agent prepared in test section 1 was oiled to the acrylic fiber strands so that the solid content adhesion amount was 1% by mass (not including the solvent). Oiling of the synthetic fiber treatment agent was carried out by an immersion method using a 4% ion-exchanged aqueous solution of the synthetic fiber treatment agent. After that, the acrylic fiber strand is dried and densified with a heating roller at 130°C, further stretched by 1.7 times between heating rollers at 170°C, and then wound around a yarn tube using a winding device. I took

Next, in step 2, yarn is unwound from the wound synthetic fiber, subjected to flameproofing treatment in an air atmosphere for 1 hour in a flameproofing furnace with a temperature gradient of 230 to 270°C, and passed through a conveying roller. Then, a flame-resistant yarn (flame-resistant fiber) was obtained by winding it around a yarn tube.

Next, in step 3, the yarn is unwound from the wound flame-resistant yarn, baked in a carbonization furnace with a temperature gradient of 300 to 1300 ° C. in a nitrogen atmosphere, converted to carbon fiber, and then formed into a yarn tube. Carbon fibers were obtained by winding.

Test category 3 (evaluation)
Regarding the treatment agents of Examples 1 to 26 and Comparative Examples 1 to 3, the bundling property of the flameproof fibers produced using the synthetic fibers to which the treatment agent was attached, the presence or absence of fusion between carbon fibers, the strength of the carbon fibers, And the presence or absence of fluff on the carbon fiber was evaluated. The procedure for each test is shown below. Also, the test results are shown in Table 1 in the columns of "flame resistant bundling", "fusion", "strength", and "fluff".

(Flame resistant convergence)
In step 2 of test section 2, the bundling state of the flame-resistant treated fibers passing through the transport rollers was visually observed, and bundling properties were evaluated according to the following criteria.

・Evaluation criteria for bundling property of flame-resistant fibers ◎ (Good): When fibers are bundled and the toe width is relatively narrow, and the toe width is constant ○ (Fair): Fibers are bundled However, when the tow width is not constant × (impossible): When the tow width is widened due to the presence of spaces in the fiber bundle without the fibers being bundled (fusion)
The carbon fibers obtained in step 3 of test section 2 were cut into 10 mm lengths and dispersed in an aqueous solution of polyoxyethylene (10) lauryl ether. After stirring for 10 minutes, the dispersed state of the fibers was visually observed, and fusion bonding was evaluated according to the following criteria.

◎ (Good): Fibers are completely uniformly dispersed and no short fiber bundles are observed. ○ (Fair): Fibers are generally uniformly dispersed, but the presence of short fiber bundles is evident. × (impossible): When the distribution of fibers is uneven and the presence of short fiber bundles is observed throughout (strength)
Using the carbon fiber obtained in step 3 of test section 2, the strength of the carbon fiber was measured according to JIS R 7606. The strength of carbon fibers was evaluated according to the following criteria.

・ Evaluation criteria for strength ◎ ◎ (excellent): strength of 4.5 GPa or more ◎ (good): strength of 4.0 GPa or more and less than 4.5 GPa ○ (acceptable): strength of 3.5 GPa or more and less than 4.0 GPa × (Not allowed): Strength less than 3.5 GPa (fluff)
In step 3 of test section 2, the carbon fibers wound around the thread tube were visually observed, and the number of fluffs per 10 minutes was evaluated according to the following criteria.

・ Evaluation criteria for fluff ◎◎ (excellent): less than 10 fluff ◎ (good): 10 or more and less than 30 fluff 〇 (acceptable): 30 or more and less than 50 fluff × (impossible) ): The number of fluffs is 50 or more From the results in Table 2, according to the present invention, the bundling property of the flame-resistant fibers can be favorably improved. Further, in the carbon fiber produced using the synthetic fiber to which the treatment agent for synthetic fiber of the present invention is adhered, the fusion between the fibers is suppressed. In addition, strength is improved and fluffing is suppressed.

TECHNICAL FIELD The present invention relates to a treatment agent for synthetic fibers and synthetic fibers.

For example, carbon fiber is produced by a spinning process of spinning acrylic resin, etc., a drying and densifying process of drying and densifying the spun fiber, and a carbon fiber precursor, which is a synthetic fiber, by drawing the dried and densified fiber. , a flameproofing treatment step of flameproofing the carbon fiber precursor, and a carbonization treatment step of carbonizing the flameproof fiber.

Synthetic fiber treatment agents are sometimes used in the process of manufacturing synthetic fibers in order to improve the bundling properties of the fibers.
Patent Document 1 discloses a fiber treatment agent as a treatment agent for synthetic fibers containing an amino-modified silicone, a surfactant, and an amine compound having a polyoxyalkylene group and two or more primary amine groups in the molecule. It is

WO2018/003347

By the way, treatment agents for synthetic fibers are required to improve bundling properties of flame-resistant synthetic fibers when synthetic fibers are flame-resistant, and to suppress fluffing of carbon fibers when flame-resistant fibers are carbonized.

The present invention has been made in view of these circumstances, and its object is to provide a treatment agent for synthetic fibers that can improve the bundling property of flame-resistant fibers and suppress the fluffing of carbon fibers. . Another object of the present invention is to provide a synthetic fiber to which this synthetic fiber treatment agent is attached.

A synthetic fiber treatment agent for solving the above problems contains a phenolamine compound and a nonionic surfactant, and the phenolamine compound is formed from the following phenol derivative, formaldehyde, and a polyamine compound. and at least one selected from the following three-component phenol derivative, formaldehyde, and polyamine compound reacted with a boron-containing compound .

Phenol derivative: A phenol in which a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less is modified.
In the synthetic fiber treatment agent, the nonionic surfactant contains 1 mol or more and 50 mol or less of an alkylene oxide having 2 or more and 4 or less carbon atoms per 1 mol of a monohydric alcohol having 4 or more and 30 or less carbon atoms. At least one of a compound added at a ratio of 1 mol or more and 50 mol or less in total of an alkylene oxide having 2 or more and 4 or less carbon atoms per 1 mol of an alkylamine having 4 or more and 30 or less carbon atoms. is preferably included.

In the synthetic fiber treatment agent, the mass ratio of the phenolamine compound and the nonionic surfactant is preferably phenolamine compound/nonionic surfactant = 5/95 or more and 95/5 or less. .

The synthetic fiber treatment agent preferably further contains Bronsted acid.
The synthetic fiber treatment agent preferably further contains an epoxy compound.

In the synthetic fiber treatment agent, the epoxy compound preferably contains at least one selected from epoxy-modified silicone and epoxy/polyether-modified silicone.

The synthetic fiber treatment agent preferably further contains at least one selected from amino-modified silicone, dimethyl silicone, and polyether-modified silicone.

In the synthetic fiber treatment agent, the synthetic fiber is preferably a carbon fiber precursor.
The gist of the synthetic fiber treatment agent for solving the above problems is that the synthetic fiber treatment agent is adhered thereto.

ADVANTAGE OF THE INVENTION According to this invention, while being able to improve the bundling property of a flameproof fiber, the fluff of carbon fiber can be suppressed.

(First embodiment)
A first embodiment of a processing agent for synthetic fibers (hereinafter also simply referred to as a processing agent) according to the present invention will be described.

The treatment agent of this embodiment contains a phenolamine compound and a nonionic surfactant.
By containing a phenolamine compound and a nonionic surfactant in the treating agent, when synthetic fibers to which the treating agent is attached are subjected to the flameproofing treatment, bundling of the flameproofed fibers can be improved. In addition, fluffing of the carbon fiber can be suppressed when the flame-resistant fiber is carbonized.

<Regarding the phenolamine compound>
The above phenolamine compound is a compound formed from the following phenol derivative, formaldehyde, and polyamine compound, and a compound formed from the following three components of the phenol derivative, formaldehyde, and polyamine compound, and a boron-containing compound. is preferably at least one selected from those reacted with

Phenol derivative: A phenol in which a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less is modified.
The phenol derivative is preferably represented by Chemical Formula 1 below.

（化１において
Ｒ^１：数平均分子量が１００以上２０００以下の炭化水素基）
上記数平均分子量が１００以上２０００以下の炭化水素基としては、特に制限されないが、例えばプロペン、ブテン、ペンテン、ヘキセン、オクテン、イソブテン、イソペンテン、イソヘキセン、イソオクテン等の重合物からなる炭化水素基が挙げられる。

(R ^{1 in Formula 1} : a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less)
The hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less is not particularly limited. be done.

The number average molecular weight is preferably 500 or more and 1,800 or less, more preferably 600 or more and 1,500 or less.
Only one R ¹ may be modified to phenol, or two or more may be modified to phenol. In the embodiment in which two or more phenols are modified, the same type of hydrocarbon groups may be modified, or different types of hydrocarbon groups may be modified. In addition, the above phenol derivative may have a functional group such as a hydrocarbon group other than R ¹ as long as it has the basic structure of phenol.

The above polyamine compound means an aliphatic hydrocarbon in which two or more primary amino groups are bonded.
The above polyamine compound is preferably represented by Chemical Formula 2 below.

（化２において
Ｘ：０以上１０以下の整数）
ポリアミン化合物の具体例としては、特に制限されないが、例えばエチレンジアミン、ジエチレントリアミン、ジプロピレントリアミン、ジブチレントリアミン、トリエチレンテトラアミン、トリプロピレンテトラアミン、トリブチレンテトラアミン、テトラエチレンペンタアミン、テトラプロピレンペンタアミン、テトラブチレンペンタアミン等が挙げられる。

(In Formula 2, X: an integer of 0 or more and 10 or less)
Specific examples of polyamine compounds include, but are not limited to, ethylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tripropylenetetraamine, tributylenetetraamine, tetraethylenepentamine, and tetrapropylenepentamine. , tetrabutylene pentamine and the like.

One of the above polyamine compounds may be used alone, or two or more of them may be used in combination.
The phenolamine compound is preferably formed by a Mannich reaction between a phenol derivative, formaldehyde, and a polyamine compound.

The phenolamine compound is preferably represented by Chemical Formula 3 or Chemical Formula 4 below.

（化３において
Ｒ^２：数平均分子量が１００以上２０００以下の炭化水素基
Ｘ：０以上１０以下の整数）

(In Formula 3, R ² : a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less X: an integer of 0 or more and 10 or less)

（化４において
Ｒ^３：数平均分子量が１００以上２０００以下の炭化水素基
Ｒ^４：数平均分子量が１００以上２０００以下の炭化水素基
Ｘ：０以上１０以下の整数）
上記フェノールアミン化合物は、上記の化３、又は化４の一方を単独で含有したものであってもよいし、化３と化４の両方を含有したものであってもよい。すなわち、フェノールアミン化合物は、化３と化４の混合物であってもよい。

(In Formula 4, R ³ : a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less R ⁴ : a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less X: an integer of 0 or more and 10 or less)
The phenolamine compound may contain either one of Chemical Formula 3 or Chemical Formula 4 alone, or may contain both Chemical Formula 3 and Chemical Formula 4. That is, the phenolamine compound may be a mixture of chemical formulas 3 and 4.

Also, the phenolamine compound may be a compound formed from three components of a phenol derivative, formaldehyde, and a polyamine compound and reacted with a boron-containing compound. For example, a boron-containing compound may be reacted with Chemical Formula 3 or Chemical Formula 4 above.

In other words, the phenolamine compound may be a borated phenolamine compound. Also, a mixture of a non-boronated phenolamine compound such as the above chemical formulas 3 and 4 and a borated phenolamine compound may be used.

Examples of the boron-containing compound include, but are not particularly limited to, boron oxide, boron halide, boric acid, boric anhydride, and borate ester.
The above boron compounds may be used singly or in combination of two or more.

The ratio of the phenol derivative, formaldehyde, and polyamine compound when forming the phenolamine compound is not particularly limited, and the ratio can be adjusted as appropriate.

As for the ratio of the phenol derivative, formaldehyde, and polyamine compound, for example, 0.7 to 3.5 equivalents of formaldehyde and 0.3 to 1.5 equivalents of polyamine compound are allowed to react with 1 equivalent of the phenol derivative. is preferred.

Further, when the phenolamine compound is obtained by reacting a boron-containing compound with a compound formed from three components of a phenol derivative, formaldehyde, and a polyamine compound, the ratio of the boron-containing compound is not particularly limited, The ratio can be adjusted as appropriate for the reaction.

As for the ratio of the boron-containing compound, for example, it is preferable to react the boron-containing compound with the phenolamine compound so that the boron content is 0.05% by mass or more and 1.5% by mass or less.

The above chemical formulas 3 and 4 as phenolamine compounds and those reacted with a boron-containing compound can be identified using, for example, a liquid chromatography-mass spectrometer (LC-MS).

<About the diluent>
As described below, the phenolamine compound is preferably used as a solution diluted with a diluent when mixed with a nonionic surfactant or the like to prepare a treatment agent.

Examples of diluents include water, organic solvents, mineral oils and the like. Specific examples of organic solvents include hexane, ethanol, isopropanol, ethylene glycol, propylene glycol, diethyl ether, toluene, xylene, dimethylformamide, methyl ethyl ketone and chloroform. Mineral oils include, for example, aromatic hydrocarbons, paraffinic hydrocarbons, naphthenic hydrocarbons, and the like. More specific examples include spindle oil and liquid paraffin. The mineral oil preferably has a viscosity of 80 to 190 redwood seconds. Commercially available products can be appropriately used as these mineral oils.

There is no restriction on the content ratio of the phenolamine compound and the diluent. Assuming that the total content of the phenolamine compound and the diluent is 100 parts by mass, the phenolamine compound can be contained at a rate of 30% by mass or more and 90% by mass or less and the diluent at a rate of 10% by mass or more and 70% by mass or less. More preferably, the content of the phenolamine compound is 40% by mass or more and 80% by mass or less, and the diluent is more preferably 20% by mass or more and 60% by mass or less.

<About nonionic surfactant>
The nonionic surfactant is not particularly limited, but a total of 1 mol or more and 50 mol or less of an alkylene oxide having 2 or more and 4 or less carbon atoms per 1 mol of a monohydric alcohol having 4 or more and 30 or less carbon atoms. At least one of a compound added and a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms in a total ratio of 1 to 50 moles per 1 mol of alkylamine having 4 to 30 carbon atoms. is preferred.

The monohydric alcohol having 4 to 30 carbon atoms may be either an aliphatic alcohol having a linear or branched structure or an aromatic alcohol. Moreover, any of primary alcohol, secondary alcohol, and tertiary alcohol may be used.

Specific examples of monohydric alcohols having 4 to 30 carbon atoms include (1) butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, and hexadecanol. straight-chain alkyl alcohols such as nol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptakosanol, octacosanol, nonacosanol, and triacontanol , (2) isobutanol, isohexanol, 2-ethylhexanol, isononanol, isodecanol, isododecanol, isotridecanol, isotetradecanol, isotriacontanol, isohexadecanol, isoheptadecanol, isooctane Decanol, isononadecanol, isoeicosanol, isoheneicosanol, isodocosanol, isotrichosanol, isotetracosanol, isopentacosanol, isohexacosanol, isoheptacosanol, isooctacosanol , isononacosanol, branched alkyl alcohols such as isopentadecanol, (3) linear alkenyl alcohols such as tetradecenol, hexadecenol, heptadecenol, octadecenol, and nonadecenol, (4) isohexadecenol, isooctadecenol, etc. branched alkenyl alcohols, (5) cyclic alkyl alcohols such as cyclopentanol and cyclohexanol, (6) aromatic alcohols such as phenol, nonylphenol, benzyl alcohol, monostyrenated phenol, distyrenated phenol, and tristyrenated phenol mentioned.

The alkylamine having 4 to 30 carbon atoms is not particularly limited, and may be any of primary amine, secondary amine and tertiary amine.
In the alkylamine having 4 to 30 carbon atoms, the alkyl group having 4 to 30 carbon atoms may be a linear or branched alkyl group. Moreover, it may be a saturated alkyl group or an unsaturated alkyl group.

Specific examples of linear alkyl groups include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl groups. , heptadecyl group, octadecyl group, icosyl group and the like.

Specific examples of branched saturated alkyl groups include isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, iso Pentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group, isoicosyl group and the like can be mentioned.

The unsaturated alkyl group may be an alkenyl group having one double bond as an unsaturated carbon bond, or an alkadienyl group or alkatrienyl group having two or more double bonds. Alternatively, an alkynyl group having one triple bond as an unsaturated carbon bond, an alkadiynyl group having two or more triple bonds, or the like may be used. Specific examples of linear unsaturated alkyl groups having one double bond in the hydrocarbon group include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl group, heptadecenyl group, octadecenyl group, icosenyl group and the like.

Specific examples of branched unsaturated alkyl groups having one double bond in the alkyl group include isooctenyl, isononenyl, isodecenyl, isoundecenyl, isododecenyl, isotridecenyl and isotetradecenyl groups. , isopentadecenyl group, isohexadecenyl group, isoheptadecenyl group, isooctadecenyl group, isoicosenyl group and the like.

Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide. Among these, those containing ethylene oxide are preferable.

The polymerization sequence of alkylene oxide is not particularly limited, and may be a random adduct or a block adduct.
The alkylene oxides having 2 to 4 carbon atoms may be used singly or in combination of two or more.

The number of moles of alkylene oxide added indicates the number of moles of alkylene oxide per 1 mole of alcohol in the starting material.
Although the mass ratio of the phenolamine compound and the nonionic surfactant is not particularly limited, it is preferably phenolamine compound/nonionic surfactant=5/95 or more and 95/5 or less.

<About Bronsted acid>
The treatment agent of the present embodiment preferably further contains a Bronsted acid.
By containing Bronsted acid, the bundling property of the flameproof fibers can be further improved.

Here, Bronsted acid is intended to mean an acid that has protons and can release or dissociate the protons in a water-containing liquid composition. It is intended to be different from acids that do not have protons, such as Lewis acids.

Specific examples of the Bronsted acid are not particularly limited, but for example, acetic acid, alkyl ether acetic acid such as polyoxyethylene (n=10) lauryl ether acetic acid, polyoxyethylene (n=4.5) lauryl ether acetic acid, oleoyl Sarcosinate, lauroyl sarcosinate, phosphoric acid esters of ethylene oxide 5-mol adducts of tridecyl alcohol, phosphoric acid esters such as hexadecyl phosphoric acid esters, lactic acid, citric acid, phosphoric acid, alkylbenzenes such as dodecylbenzenesulfonic acid Sulfonic acid, sulfuric acid and the like can be mentioned.

The Bronsted acids may be used singly or in combination of two or more.
The content of Bronsted acid in the treatment agent is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less.

<About epoxy compounds>
The treatment agent of the present embodiment preferably further contains an epoxy compound.
By containing an epoxy compound, when synthetic fibers to which a treatment agent is attached are used to produce carbon fibers, fluffing of the carbon fibers can be suitably suppressed.

The epoxy compound is not particularly limited, and preferably contains at least one selected from epoxy-modified silicone and epoxy/polyether-modified silicone.

When the epoxy compound contains at least one selected from the above-mentioned epoxy-modified silicone and epoxy-polyether-modified silicone, it is possible to more preferably suppress fluff of the carbon fibers.

Specific examples of the epoxy compound include, for example, a side chain type alicyclic epoxy-modified silicone having a kinematic viscosity at 25°C of 6000 ^{mm 2} /s and an equivalent weight of 3700 g/mol; a side chain type glycidyl epoxy-modified silicone having a kinematic viscosity of 3300 g/mol; a kinematic viscosity at 25°C of 120 ^{mm 2} /s; an equivalent weight of 2700 g/mol; A side chain type glycidyl epoxy polyether-modified silicone having an equivalent weight of 2800 g/mol, a kinematic viscosity of 5000 mm ² /s at 25°C, a side chain type alicyclic epoxy-modified silicone having an equivalent weight of 4200 g/mol, and a kinematic viscosity at 25°C. is 3100 mm ² /s and the equivalent weight is 10200 g/mol side chain type glycidyl epoxy polyether modified silicone, bisphenol A diglycidyl ether (average molecular weight 370), bisphenol A diglycidyl ether (average molecular weight 470), bisphenol F diglycidyl ether (average molecular weight: 340), tetraglycidyldiaminodiphenylmethane, glycidyl etherate of polyglycerin (average molecular weight: 1000), and the like.

The epoxy compounds may be used singly or in combination of two or more. The kinematic viscosity at 25°C of an epoxy compound or the like can be measured by a known method under conditions of 25°C using a Canon Fenske viscometer.

Although the content of the epoxy compound in the treatment agent is not particularly limited, it is preferably 1% by mass or more and 50% by mass or less, and more preferably 3% by mass or more and 20% by mass or less.
<About other silicones>
The treatment agent preferably further contains a silicone other than the epoxy-modified silicone and the epoxy/polyether-modified silicone (hereinafter also referred to as "other silicone"). By containing other silicones, as described later, the strength of carbon fibers produced using synthetic fibers to which a treatment agent is attached can be further improved.

In addition, the treatment agent contains other silicone and the above-mentioned epoxy compound, so that when carbon fibers are produced using synthetic fibers to which the treatment agent is attached, the carbon fibers are more preferably fused together. can be suppressed.

The other silicone is preferably at least one selected from amino-modified silicone, dimethyl silicone, and polyether-modified silicone.
Specific examples of other silicones include, for example, a diamine-type amino-modified silicone having a kinematic viscosity at 25° C. of ²⁵⁰ mm ² /s and an equivalent weight of 7600 g/mol; mol, a monoamine-type amino-modified silicone having a kinematic viscosity at 25° C. of 1700 mm ² /s and an equivalent weight of 3800 g/mol, a kinematic viscosity at 25° C. of 80 mm ² /s and an equivalent weight of 4000 g/ mol of diamine-type amino-modified silicone, dimethyl silicone with kinematic viscosity at 25°C of 5000 mm ² /s, kinematic viscosity at 25°C of 1700 mm ² /s, ethylene oxide/propylene oxide = 40/60, silicone/polyether mass ratio = 20/80 polyether-modified silicone and the like.

(Second embodiment)
A second embodiment of the synthetic fiber according to the present invention will be described. The synthetic fiber of this embodiment is a synthetic fiber to which the treatment agent of the first embodiment is attached. Specific examples of synthetic fibers are not particularly limited, and include (1) polyester fibers such as polyethylene terephthalate, polypropylene terephthalate and polylactate; (4) polyolefin fibers such as polyethylene and polypropylene; (5) cellulose fibers; and (6) lignin fibers.

As the synthetic fiber, a resin-made carbon fiber precursor that becomes a carbon fiber through a carbonization treatment step described later is preferable. The resin constituting the carbon fiber precursor is not particularly limited, but examples thereof include acrylic resins, polyethylene resins, phenol resins, cellulose resins, lignin resins, and pitch.

Although there is no particular limitation on the proportion of the treatment agent of the first embodiment attached to the synthetic fibers, it is preferable to attach the treatment agent (not containing a solvent) to the synthetic fibers in an amount of 0.1 to 2% by mass. , 0.3 to 1.2% by mass.

Examples of the form in which the processing agent of the first embodiment is attached to the fibers include an organic solvent solution, an aqueous liquid, and the like.
As a method for attaching the treatment agent to the synthetic fibers, for example, a known method such as a dipping method, a spray method, a roller method, or a metering pump is applied using an organic solvent solution, an aqueous solution, or the like of the treatment agent of the first embodiment. A method of adhering by the guide lubrication method or the like used can be applied.

A treatment agent according to the present invention and a method for producing carbon fibers using synthetic fibers to which the treatment agent is attached will be described.
The method for producing the carbon fiber preferably includes steps 1 to 3 below.

Step 1: A spinning step in which synthetic fibers are spun and the treatment agent of the first embodiment is attached.
Step 2: A flameproofing step of converting the synthetic fiber obtained in the step 1 into a flameproof fiber in an oxidizing atmosphere at 200 to 300°C, preferably 230 to 270°C.

Step 3: A carbonization step of further carbonizing the flame-resistant fiber obtained in the step 2 in an inert atmosphere at 300 to 2000°C, preferably 300 to 1300°C.
The spinning process further includes a wet spinning process of dissolving a resin in a solvent and spinning, a dry densification process of drying and densifying the wet-spun synthetic fibers, and a drawing process of drawing the dry densified synthetic fibers. It is preferable to have

The temperature of the dry densification step is not particularly limited, but it is preferable to heat the synthetic fibers that have undergone the wet spinning step at, for example, 70 to 200°C. The timing of applying the treatment agent to the synthetic fibers is not particularly limited, but it is preferably between the wet spinning process and the dry densification process.

The oxidizing atmosphere in the flameproofing treatment step is not particularly limited, and for example, an air atmosphere can be adopted.
The inert atmosphere in the carbonization treatment step is not particularly limited, and for example, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or the like can be adopted.

According to the treatment agent and synthetic fiber of the present embodiment, the following effects can be obtained.
(1) The treatment agent contains a phenolamine compound and a nonionic surfactant. Therefore, when the synthetic fibers to which the treating agent is attached are subjected to the flameproofing treatment, the bundling property of the flameproofing fibers can be improved. In addition, fluffing of the carbon fiber can be suppressed when the flame-resistant fiber is carbonized.

(2) The treating agent further contains Bronsted acid. Therefore, the bundling property of the flameproof fibers can be further improved.
(3) The treating agent contains an epoxy compound. Therefore, when carbon fibers are produced using synthetic fibers to which the treatment agent is attached, fluffing of the carbon fibers can be suitably suppressed.

(4) The treatment agent contains other silicones and epoxy compounds. Therefore, when carbon fibers are manufactured using synthetic fibers to which a treatment agent is attached, it is possible to more preferably suppress fusion between carbon fibers.

The above embodiment can be implemented with the following modifications. The above embodiments and the following modifications can be combined with each other within a technically consistent range.
- In the present embodiment, the treatment agent is attached to the synthetic fibers between the wet spinning process and the dry densification process, but the present invention is not limited to this aspect. The treating agent may be attached to the synthetic fibers between the drying densification step and the drawing step, or the treating agent may be attached to the synthetic fibers between the drawing step and the flameproofing step.

- In the present embodiment, for example, the synthetic fiber may be a fiber that is subjected to the flameproofing treatment, but is not subjected to the carbonization treatment. Also, the fiber may be a fiber that is not subjected to both the flameproofing treatment step and the carbonization treatment step.

・The processing agent of the present embodiment contains a stabilizer, an antistatic agent, an antistatic agent, a binder, an antioxidant, and an ultraviolet absorber to maintain the quality of the processing agent within a range that does not impede the effects of the present invention. Ingredients commonly used in treatment agents, such as agents and antifoaming agents (silicone compounds), may also be added.

Examples will be given below in order to make the configuration and effect of the present invention more specific, but the present invention is not limited to these examples. In the following examples and comparative examples, "part" means "mass part" and "%" means "mass%".

Test category 1 (preparation of treatment agents for synthetic fibers)
(Example 1)
A solution (A-1) of a phenolamine compound containing 70 parts of the phenolamine compound (a1-1) and 30 parts of the diluent (a2-1) shown in Table 1 was prepared by the following method. did.

<Solution of phenolamine compound (A-1)>
First, 800 parts (1 equivalent) of a phenol modified with a polybutenyl group where the polybutene portion has a number average molecular weight of 1500, 52 parts (0.7 equivalent) of triethylenetetramine, and 368 parts of mineral oil of 100 redwood seconds. mixed with. To the resulting mixture, 30 parts of a 50% formaldehyde aqueous solution (equivalent to 15 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-1).

Phenolamine compound solutions (A-2) to (A-12) were prepared by the following method.
<Solution of phenolamine compound (A-2)>
100 parts of the phenolamine compound solution (A-1) was reacted with 1.1 parts of boric acid to prepare a phenolamine compound solution (A-2) having a boron content of 0.2% by mass.

<Solution of phenolamine compound (A-3)>
730 parts (1 equivalent) of a phenol modified with polybutenyl groups where the polybutene portion has a number average molecular weight of 1200, 58 parts (1 equivalent) of diethylenetriamine, and 530 parts of 80 redwood second liquid paraffin were mixed. To the resulting mixture, 34 parts of a 50% formaldehyde aqueous solution (equivalent to 17 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-3).

<Solution of phenolamine compound (A-4)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups where the polybutene portion has a number average molecular weight of 600, 102 parts (0.6 equivalent) of triethylenetetraamine, and 916 parts of 150 redwood second mineral oil. Mixed. To the resulting mixture, 70 parts of a 50% formaldehyde aqueous solution (equivalent to 35 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-4).

<Solution of phenolamine compound (A-5)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups where the polybutene portion has a number average molecular weight of 1500, 47 parts (0.5 equivalent) of tripropylenetetraamine, and 213 parts of 100 redwood second liquid paraffin. Mixed. To the resulting mixture, 30 parts of a 50% formaldehyde aqueous solution (equivalent to 15 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-5).

<Solution of phenolamine compound (A-6)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups wherein the polybutene portion has a number average molecular weight of 1500, 66 parts (0.9 equivalent) of triethylenetetraamine, and 872 parts of 120 redwood second mineral oil. Mixed. To the resulting mixture, 30 parts of a 50% formaldehyde aqueous solution (equivalent to 15 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-6).

<Solution of phenolamine compound (A-7)>
100 parts of the phenolamine compound solution (A-6) was reacted with 5.7 parts of boric acid to prepare a phenolamine compound solution (A-7) having a boron content of 1.0% by mass.

<Solution of phenolamine compound (A-8)>
800 parts (1 equivalent) of a phenol modified with polyisobutenyl groups wherein the polyisobutylene portion has a number average molecular weight of 900, 130 parts (1.1 equivalent) of triethylenetetramine, and 1410 parts of 190 redwood second mineral oil were mixed. To the resulting mixture, 150 parts of a 50% formaldehyde aqueous solution (equivalent to 75 parts of formaldehyde, 3.1 equivalents) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-8).

<Solution of phenolamine compound (A-9)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups wherein the polybutene portion has a number average molecular weight of 600, 175 parts (0.8 equivalent) of tetraethylenepentamine, and 423 parts of 100 redwood second mineral oil. Mixed. To the resulting mixture, 62 parts of a 50% formaldehyde aqueous solution (equivalent to 31 parts of formaldehyde, 0.9 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-9).

<Solution of phenolamine compound (A-10)>
800 parts (1 equivalent) of a phenol modified with polybutenyl groups where the polybutene portion has a number average molecular weight of 1000, 31 parts (0.7 equivalent) of ethylenediamine, and 840 parts of 120 redwood second mineral oil were mixed. To the resulting mixture, 44 parts of a 50% formaldehyde aqueous solution (equivalent to 22 parts of formaldehyde, 1 equivalent) was added dropwise over 1 hour, followed by reaction at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-10).

<Solution of phenolamine compound (A-11)>
800 parts (1 equivalent) of a phenol modified with polypropenyl groups wherein the polypropylene portion has a number average molecular weight of 1500; 30 parts of a 50% formaldehyde aqueous solution (equivalent to 15 parts of formaldehyde, 1 equivalent) was added dropwise to the resulting mixture over 1 hour, and then reacted at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-11).

<Solution of phenolamine compound (A-12)>
800 parts (1 equivalent) of octyl-modified phenol, 260 parts (0.7 equivalent) of diethylenetriamine, and 871 parts of 120 redwood second mineral oil were mixed. After 276 parts of a 50% formaldehyde aqueous solution (equivalent to 108 parts of formaldehyde, 1 equivalent) was added dropwise to the resulting mixture over 1 hour, the mixture was reacted at 100° C. for 3 hours under a nitrogen stream. The temperature was raised to 200° C., and unreacted substances and generated water were removed under reduced pressure. Thereafter, the temperature was lowered and filtered to prepare a phenolamine compound solution (A-12).

The type and content of the phenolamine compound and the type and content of the diluent are as shown in the "phenolamine compound" column and the "diluent" column of Table 1, respectively.

（フェノールアミン化合物）
ａ１－１：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物
ａ１－２：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物をホウ酸と反応させた化合物（ホウ素含有量：０．２質量％）
ａ１－３：ポリブテン部分の数平均分子量が１２００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／ジエチレントリアミンを反応させて得られた化合物
ａ１－４：ポリブテン部分の数平均分子量が６００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物
ａ１－５：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリプロピレンテトラアミンを反応させて得られた化合物
ａ１－６：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物
ａ１－７：ポリブテン部分の数平均分子量が１５００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物をホウ酸と反応させた化合物（ホウ素含有量：１．０質量％）
ａ１－８：ポリイソブチレン部分の数平均分子量が９００であるポリイソブテニル基で変性されたフェノール／ホルムアルデヒド／トリエチレンテトラアミンを反応させて得られた化合物
ａ１－９：ポリブテン部分の数平均分子量が６００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／テトラエチレンペンタアミンを反応させて得られた化合物
ａ１－１０：ポリブテン部分の数平均分子量が１０００であるポリブテニル基で変性されたフェノール／ホルムアルデヒド／エチレンジアミンを反応させて得られた化合物
ａ１－１１：ポリプロピレン部分の数平均分子量が１５００であるポリプロペニル基で変性されたフェノール／ホルムアルデヒド／トリブチレンテトラアミンを反応させて得られた化合物
ａ１－１２：オクチル基で変性されたフェノール／ホルムアルデヒド／ジエチレントリアミンを反応させて得られた化合物
（希釈剤）
ａ２－１：鉱物油（レッドウッド粘度計での粘度が１００秒）
ａ２－２：流動パラフィン（レッドウッド粘度計での粘度が８０秒）
ａ２－３：鉱物油（レッドウッド粘度計での粘度が１５０秒）
ａ２－４：流動パラフィン（レッドウッド粘度計での粘度が１００秒）
ａ２－５：鉱物油（レッドウッド粘度計での粘度が１２０秒）
ａ２－６：鉱物油（レッドウッド粘度計での粘度が１９０秒）
次に、表２に示される各成分を用いて、フェノールアミン化合物の溶液（Ａ－１）が６０部、非イオン性界面活性剤（Ｂ１－１）が２０部、ブレンステッド酸（Ｃ－１）が０．５部、エポキシ化合物（Ｄ－１）が７．５部、その他のシリコーン（Ｅ－１）が１０部、その他化合物が２部となるようにビーカーに加えた。これらをよく撹拌して合成繊維用処理剤を調製した。

(Phenolamine compound)
a1-1: A compound obtained by reacting phenol/formaldehyde/triethylenetetramine modified with a polybutenyl group having a polybutene moiety with a number average molecular weight of 1,500 a1-2: A polybutene moiety having a number average molecular weight of 1,500 A compound obtained by reacting a compound obtained by reacting phenol/formaldehyde/triethylenetetraamine modified with a polybutenyl group and reacting it with boric acid (boron content: 0.2% by mass)
a1-3: A compound obtained by reacting phenol/formaldehyde/diethylenetriamine modified with a polybutenyl group whose polybutene moiety has a number average molecular weight of 1200 a1-4: A polybutenyl group whose polybutene moiety has a number average molecular weight of 600 Compound obtained by reacting modified phenol/formaldehyde/triethylenetetramine a1-5: phenol/formaldehyde/tripropylenetetramine modified with a polybutenyl group having a polybutene moiety with a number average molecular weight of 1,500 was reacted. Compound a1-6 obtained by reacting polybutenyl group-modified phenol/formaldehyde/triethylenetetramine having a polybutene moiety with a number average molecular weight of 1500 a1-7: Number average polybutene moiety A compound obtained by reacting a compound obtained by reacting polybutenyl group-modified phenol/formaldehyde/triethylenetetramine having a molecular weight of 1500 with boric acid (boron content: 1.0% by mass)
a1-8: A compound obtained by reacting phenol/formaldehyde/triethylenetetramine modified with a polyisobutenyl group having a polyisobutylene moiety with a number average molecular weight of 900 a1-9: A polybutene moiety having a number average molecular weight of 600 Compound obtained by reacting phenol/formaldehyde/tetraethylenepentamine modified with a certain polybutenyl group a1-10: Reaction of phenol/formaldehyde/ethylenediamine modified with a polybutenyl group having a polybutene moiety with a number average molecular weight of 1000 Compound a1-11 obtained by reacting polypropenyl group-modified phenol/formaldehyde/tributylene tetraamine in which the polypropylene portion has a number average molecular weight of 1500 a1-12: Compound obtained by reacting with octyl group Compound obtained by reacting modified phenol/formaldehyde/diethylenetriamine (diluent)
a2-1: Mineral oil (viscosity with Redwood viscometer is 100 seconds)
a2-2: Liquid paraffin (viscosity with Redwood viscometer is 80 seconds)
a2-3: Mineral oil (viscosity in Redwood viscometer is 150 seconds)
a2-4: liquid paraffin (viscosity of 100 seconds with a Redwood viscometer)
a2-5: Mineral oil (viscosity on Redwood viscometer is 120 seconds)
a2-6: Mineral oil (190 seconds viscosity with Redwood viscometer)
Next, using each component shown in Table 2, 60 parts of phenolamine compound solution (A-1), 20 parts of nonionic surfactant (B1-1), Bronsted acid (C-1 ), 7.5 parts of the epoxy compound (D-1), 10 parts of the other silicone (E-1), and 2 parts of the other compound were added to the beaker. These were thoroughly stirred to prepare a synthetic fiber treatment agent.

(Examples 2 to 26 and Comparative Examples 1 to 3)
A solution of each phenolamine compound of Examples 2 to 26 and Comparative Examples 1 to 3 was prepared in the same manner as in Example 1 using each component shown in Tables 1 and 2. Type and content of phenolamine compound solution, type and content of nonionic surfactant, type and content of Bronsted acid, type and content of epoxy compound, and other silicones in the treatment agent of each example The type and content of other compounds, the type and content of other compounds, and the mass ratio of the succinimide compound and the nonionic surfactant are shown in Table 2, "Solution of phenolamine compound" column, ” column, “Bronsted acid” column, “epoxy compound” column, “other silicone” column, “other compound” column, and “succinimide compound / nonionic surfactant” column, respectively. .

表２の記号欄に記載するＢ１－１～Ｂ１－９、Ｂ２－１～Ｂ２－３、Ｃ－１～Ｃ－１１、Ｄ－１～Ｄ－１１、Ｅ－１～Ｅ－６、Ｆ－１～Ｆ－５の各成分の詳細は以下のとおりである。

B1-1 to B1-9, B2-1 to B2-3, C-1 to C-11, D-1 to D-11, E-1 to E-6, F- described in the symbol column of Table 2 The details of each component of 1 to F-5 are as follows.

(Nonionic surfactant)
B1-1: Compound obtained by adding 9 mol of ethylene oxide to 1 mol of dodecyl alcohol B1-2: Compound obtained by adding 12 mol of ethylene oxide to 1 mol of isododecyl alcohol B1-3: 1 mol of tetradecyl alcohol B1-4: Compound obtained by adding 7 mol of ethylene oxide to 1 mol of tetradecyl alcohol B1-5: 15 mol of ethylene oxide to 1 mol of pentadecyl alcohol Added compound B1-6: Compound obtained by adding 15 mol of ethylene oxide to 1 mol of tetradecyl alcohol and then adding 18 mol of propylene oxide B1-7: Ethylene to 1 mol of secondary tridecyl alcohol Compound to which 9 mol of oxide was added B1-8: Compound to which 2 mol of ethylene oxide and 6 mol of propylene oxide were randomly added to 1 mol of dodecyl alcohol B1-9: Ethylene oxide to 1 mol of tristyrenated phenol 15 mol of and 9 mol of propylene oxide are added B2-1: A compound in which 4 mol of ethylene oxide is added to 1 mol of dodecylamine B2-2: 8 mol of ethylene oxide is added to 1 mol of dodecylamine Compound B2-3: A compound obtained by adding 15 mol of ethylene oxide to 1 mol of octadecylamine (Bronsted acid)
C-1: acetic acid C-2: polyoxyethylene (n = 10) lauryl ether acetic acid C-3: polyoxyethylene (n = 4.5) lauryl ether acetic acid C-4: oleoyl sarcosinate C-5: Lauroyl sarcosinate C-6: phosphate ester of tridecyl alcohol ethylene oxide 5 mole adduct C-7: hexadecyl phosphate ester C-8: lactic acid C-9: citric acid C-10: phosphoric acid C- 11: Dodecylbenzenesulfonic acid (epoxy compound)
D-1: Side chain type alicyclic epoxy-modified silicone having a kinematic viscosity at 25°C of 6000 mm ² /s and an equivalent weight of 3700 g/mol D-2: A kinematic viscosity at 25°C of 8000 mm ² /s and an equivalent weight of 3300 g/mol mol side chain type glycidyl epoxy-modified silicone D-3: kinematic viscosity at 25° C. is 120 mm ² /s and equivalent weight is 2700 g/mol double-ended glycidyl epoxy-modified silicone D-4: kinematic viscosity at 25° C. is 2800 mm ² /s, equivalent weight is 2800 g/mol side chain type glycidyl epoxy polyether-modified silicone D-5: side chain type alicyclic epoxy-modified silicone with kinematic viscosity at 25° C. of 5000 mm ² /s and equivalent weight of 4200 g/mol Silicone D-6: Side chain type glycidyl epoxy polyether-modified silicone having a kinematic viscosity at 25°C of 3100 mm ² /s and an equivalent weight of 10200 g/mol D-7: Bisphenol A diglycidyl ether (average molecular weight 370)
D-8: bisphenol A diglycidyl ether (average molecular weight 470)
D-9: Bisphenol F diglycidyl ether (average molecular weight 340)
D-10: Tetraglycidyldiamine diphenylmethane D-11: Glycidyl etherate of polyglycerin (average molecular weight 1000)
(other silicones)
E-1: A diamine-type amino-modified silicone having a kinematic viscosity at 25°C of 250 mm ² /s and an equivalent weight of 7600 g/mol E-2: A kinematic viscosity at 25°C of 1300 mm ² /s and an equivalent weight of 1700 g/mol Diamine-type amino-modified silicone E-3: Monoamine-type amino-modified silicone with a kinematic viscosity of 1700 mm ² /s at 25°C and an equivalent weight of 3800 g/mol E-4: Kinematic viscosity at 25°C of 80 mm ² /s and an equivalent diamine type amino-modified silicone E-5: dimethyl silicone having a kinematic viscosity of 5000 mm ² /s at 25° C. E-6: kinematic viscosity of 1700 mm ² /s at 25° C., ethylene oxide/propylene oxide = 40/60, polyether-modified silicone with a silicone/polyether mass ratio of 20/80 (Other compounds)
F-1: Polyethylene glycol having a molecular weight of 600 with 3-aminopropyl groups added to both ends F-2: Didodecyl ester of a bisphenol A ethylene oxide 2-mol adduct F-3: 1-ethyl-2-( heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium ethyl sulfate F-4: trimethyloctylammonium dimethyl phosphate F-5: isotridecyl isostearate Test category 2 ( manufacturing of synthetic fibers and carbon fibers)
Synthetic fibers and carbon fibers were produced using the synthetic fiber treatment agent prepared in Test Section 1.

First, as step 1, an acrylic resin was wet-spun. Specifically, a copolymer composed of 95% by mass of acrylonitrile, 3.5% by mass of methyl acrylate, and 1.5% by mass of methacrylic acid and having an intrinsic viscosity of 1.80 was dissolved in dimethylacetamide (DMAC) to give a polymer concentration of was 21.0% by mass and a spinning dope having a viscosity of 500 poise at 60°C was prepared. The spinning stock solution was discharged from a spinneret with a hole diameter (inner diameter) of 0.075 mm and a hole number of 12,000 at a draft ratio of 0.8 into a coagulation bath of 70 mass % aqueous solution of DMAC kept at a spinning bath temperature of 35°C.

The coagulated yarn was desolvated in a washing tank and simultaneously stretched 5 times to prepare a water-swollen acrylic fiber strand (raw material fiber). The synthetic fiber treatment agent prepared in test section 1 was oiled to the acrylic fiber strands so that the solid content adhesion amount was 1% by mass (not including the solvent). Oiling of the synthetic fiber treatment agent was carried out by an immersion method using a 4% ion-exchanged aqueous solution of the synthetic fiber treatment agent. After that, the acrylic fiber strand is dried and densified with a heating roller at 130°C, further stretched by 1.7 times between heating rollers at 170°C, and then wound around a yarn tube using a winding device. I took

Next, in step 2, yarn is unwound from the wound synthetic fiber, subjected to flameproofing treatment in an air atmosphere for 1 hour in a flameproofing furnace with a temperature gradient of 230 to 270°C, and passed through a conveying roller. Then, a flame-resistant yarn (flame-resistant fiber) was obtained by winding it around a yarn tube.

Next, in step 3, the yarn is unwound from the wound flame-resistant yarn, baked in a carbonization furnace with a temperature gradient of 300 to 1300 ° C. in a nitrogen atmosphere, converted to carbon fiber, and then formed into a yarn tube. Carbon fibers were obtained by winding.

Test category 3 (evaluation)
Regarding the treatment agents of Examples 1 to 26 and Comparative Examples 1 to 3, the bundling property of the flameproof fibers produced using the synthetic fibers to which the treatment agent was attached, the presence or absence of fusion between carbon fibers, the strength of the carbon fibers, And the presence or absence of fluff on the carbon fiber was evaluated. The procedure for each test is shown below. Also, the test results are shown in Table 1 in the columns of "flame resistant bundling", "fusion", "strength", and "fluff".

(Flame resistant convergence)
In step 2 of test section 2, the bundling state of the flame-resistant treated fibers passing through the transport rollers was visually observed, and bundling properties were evaluated according to the following criteria.

・Evaluation criteria for bundling property of flame-resistant fibers ◎ (Good): When fibers are bundled and the toe width is relatively narrow, and the toe width is constant ○ (Fair): Fibers are bundled However, when the tow width is not constant × (impossible): When the tow width is widened due to the presence of spaces in the fiber bundle without the fibers being bundled (fusion)
The carbon fibers obtained in step 3 of test section 2 were cut into 10 mm lengths and dispersed in an aqueous solution of polyoxyethylene (10) lauryl ether. After stirring for 10 minutes, the dispersed state of the fibers was visually observed, and fusion bonding was evaluated according to the following criteria.

◎ (Good): Fibers are completely uniformly dispersed and no short fiber bundles are observed. ○ (Fair): Fibers are generally uniformly dispersed, but the presence of short fiber bundles is evident. × (impossible): When the distribution of fibers is uneven and the presence of short fiber bundles is observed throughout (strength)
Using the carbon fiber obtained in step 3 of test section 2, the strength of the carbon fiber was measured according to JIS R 7606. The strength of carbon fibers was evaluated according to the following criteria.

・ Evaluation criteria for strength ◎ ◎ (excellent): strength of 4.5 GPa or more ◎ (good): strength of 4.0 GPa or more and less than 4.5 GPa ○ (acceptable): strength of 3.5 GPa or more and less than 4.0 GPa × (Not allowed): Strength less than 3.5 GPa (fluff)
In step 3 of test section 2, the carbon fibers wound around the thread tube were visually observed, and the number of fluffs per 10 minutes was evaluated according to the following criteria.

・ Evaluation criteria for fluff ◎◎ (excellent): less than 10 fluff ◎ (good): 10 or more and less than 30 fluff 〇 (acceptable): 30 or more and less than 50 fluff × (impossible) ): The number of fluffs is 50 or more From the results in Table 2, according to the present invention, the bundling property of the flame-resistant fibers can be favorably improved. Further, in the carbon fiber produced using the synthetic fiber to which the treatment agent for synthetic fiber of the present invention is adhered, the fusion between the fibers is suppressed. In addition, strength is improved and fluffing is suppressed.

Claims (10)

A synthetic fiber treatment agent comprising a phenolamine compound and a nonionic surfactant. The phenolamine compound is
A compound formed from the following phenol derivative, formaldehyde, and a polyamine compound, and a compound formed from the following three components of a phenol derivative, formaldehyde, and a polyamine compound, which is reacted with a boron-containing compound The treatment agent for synthetic fibers according to claim 1, which is at least one selected.
Phenol derivative: A phenol in which a hydrocarbon group having a number average molecular weight of 100 or more and 2000 or less is modified. The nonionic surfactant is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to 1 mol of a monohydric alcohol having 4 to 30 carbon atoms in a total ratio of 1 to 50 moles, and Claim 1 or 2, comprising at least one compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to 1 mol to 1 mol of an alkylamine having 4 to 30 carbon atoms in a total amount of 1 to 50 moles. The treatment agent for synthetic fibers described. The mass ratio of the phenolamine compound and the nonionic surfactant is phenolamine compound/nonionic surfactant = 5/95 or more and 95/5 or less, according to any one of claims 1 to 3. The treatment agent for synthetic fibers described. The treatment agent for synthetic fibers according to any one of claims 1 to 4, further comprising Bronsted acid. The treatment agent for synthetic fibers according to any one of claims 1 to 5, further comprising an epoxy compound. 7. The synthetic fiber treatment agent according to claim 6, wherein the epoxy compound contains at least one selected from epoxy-modified silicone and epoxy-polyether-modified silicone. The synthetic fiber treatment agent according to any one of claims 1 to 7, further comprising at least one selected from amino-modified silicone, dimethyl silicone, and polyether-modified silicone. The synthetic fiber treatment agent according to any one of claims 1 to 8, wherein the synthetic fiber is a carbon fiber precursor. A synthetic fiber to which the synthetic fiber treatment agent according to any one of claims 1 to 9 is adhered.